两种MOFs材料用于O2/He吸附分离的模拟分析

doi:10.16085/j.issn.1000-6613.2023-1063

摘要/Abstract

摘要：

应用分子模拟中的蒙特卡洛方法研究了HKUST-1和UiO66两种金属-有机框架（MOFs）材料对O₂/He混合气体的吸附分离效果。对两种材料在150K、200K和298K三种不同温度下吸附He和O₂纯气体的吸附等温线进行了模拟计算，同时计算了相应的吸附热和吸附势能分布，然后使用理想溶液吸附理论（IAST），对三种温度下不同含氦量的O₂/He混合气体在两种MOFs材料中的吸附选择性进行了计算。结果表明：两种材料均对O₂表现出明显优先吸附的特点，对于He体积分数20%、50%和80%的三种O₂/He混合气体，三种温度下HKUST-1对O₂相对于He的选择性吸附系数总体上高于UiO66。两种材料在较低温度下表现出的选择吸附性更加明显，且对O₂相对于He的选择性吸附系数均随压力的提高而降低，同时该系数还随混合气体含氦量增加而提高。针对这些现象，对计算出的吸附热和吸附势能分布曲线进行了分析。

关键词: 分离, 分子模拟, 吸附, 金属-有机框架, 氦气, 氧气

Abstract:

The effects of adsorption and separation of O₂/He mixture by two metal-organic frame (MOFs) materials, HKUST-1 and UiO66, were studied by using the Monte Carlo method in molecular simulation. The adsorption isotherms of He and O₂ pure gas were calculated at different temperatures of 150K, 200K and 298K, and the corresponding adsorption heat and adsorption potential energy distribution were also calculated, and then the Idea Adsorbed Solution Theory (IAST) was used to calculate the adsorption selectivity of O₂/He mixture with different helium content in the two MOFs materials. The results showed that both materials exhibited a clear preferential adsorption characteristic of O₂. For three types of O₂/He mixed gases with He volume fraction of 20%, 50% and 80% , the selective adsorption coefficient of HKUST-1 for O₂relative to He was generally higher than UiO66 at all three temperatures. Both materials indicated more significant selective adsorption at lower temperatures and their selective adsorption coefficients for O₂ relative to He decreased with increasing pressure. At the same time, this coefficient also increased with increasing helium content in the mixed gas. In response to these phenomena, the calculated adsorption heat and adsorption potential energy distribution curves were analyzed.

Key words: separation, molecular simulation, adsorption, metal-organic frame, helium, oxygen

中图分类号:

TQ021.4

崔守成, 徐洪波, 彭楠. 两种MOFs材料用于O₂/He吸附分离的模拟分析[J]. 化工进展, 2023, 42(S1): 382-390.

CUI Shoucheng, XU Hongbo, PENG Nan. Simulation analysis of two MOFs materials for O₂/He adsorption separation[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 382-390.

图/表 10

图1 HKUST-1和UiO66结构示意图

表1 两种MOFs材料的比表面积、孔体积与孔隙率

材料	He			O₂
材料	S/m²·g^-1	V_F/cm³·g^-1	R/%	S/m²·g^-1	V_F/cm³·g^-1	R/%
HKUST-1	2724.76	0.76	69.9	2700.50	0.74	68.5
UiO66	4197.08	0.45	43.6	3355.84	0.36	34.3

图2 HKUST-1和UiO66吸附O2和He纯气体的吸附等温线

表2 两种MOFs材料对O2和He纯气体吸附数据的拟合参数

材料	温度/K	O₂				He
材料	温度/K	q_s/mmol·g^-1	b/bar^-1	n	R²	k_H/mmol·g^-1·bar^-1	R²
HKUST-1	150	20.79	0.23	1.35	0.9993	0.1524	0.9997
	200	18.21	0.04	1.18	0.9996	0.0807	0.9998
	298	15.60	0.0084	1.10	0.9999	0.0394	1.0000
UiO66	150	8.97	0.26	1.02	0.9986	0.0759	0.9998
	200	7.08	0.05	0.90	1.0000	0.0384	0.9999
	298	4.99	0.0082	0.97	0.9996	0.0180	0.9998

图3 HKUST-1对O2/He混合气体的选择性吸附系数SO2/He

图4 UiO66对O2/He混合气体的吸附等温线选择性吸附系数SO2/He

图5 IAST预测与GCMC模拟所得UiO66对O2/He混合气体吸附等温线对比

图6 不同温度下HKUST-1和UiO66对O2和He的吸附势能分布

图7 200K、10kPa下HKUST-1和UiO66中O2和He的概率分布

图8 不同温度下HKUST-1和UiO66对O2和He的等量吸附热

参考文献 23

1	JAMDADE Shubham, GURNANI Rishi, FANG Hanjun, et al. Identifying high-performance metal-organic frameworks for low-temperature oxygen recovery from helium by computational screening[J]. Industrial & Engineering Chemistry Research, 2023, 62(4): 1927-1935.
2	许光, 李玉宏, 王宗起, 等. 我国氦气资源调查评价进展[J]. 地质学报, 2023, 97(5): 1711-1716.
	XU Guang, LI Yuhong, WANG Zongqi, et al. Progress in investigation and evaluation of helium resources in China[J]. Acta Geologica Sinica, 2023, 97(5): 1711-1716.
3	马蕾, 张飞飞, 宋志强, 等. 金属有机骨架材料用于吸附分离CH₄和N₂的研究进展[J]. 化工进展, 2021, 40(9): 5107-5117.
	MA Lei, ZHANG Feifei, SONG Zhiqiang, et al. Development of metal-organic frameworks in adsorptive separation of CH₄ and N₂ [J]. Chemical Industry and Engineering Progress, 2021, 40(9): 5107-5117.
4	YAN Yaling, SHI Zenan, LI Huilin, et al. Machine learning and in-silico screening of metal-organic frameworks for O₂/N₂ dynamic adsorption and separation[J]. Chemical Engineering Journal, 2022, 427: 131604.
5	Pezhman ZARABADI-POOR, MAREK Radek. Metal-organic frameworks for helium recovery from natural gas via N₂/He separation: A computational screening[J]. The Journal of Physical Chemistry C, 2019, 123(6): 3469-3475.
6	席国君, 刘子涵, 雷广平. FeTPPs-CuBTC协同强化低浓度煤层气吸附分离[J]. 化工学报, 2022, 73(9): 3940-3949.
	XI Guojun, LIU Zihan, LEI Guangping. Enhanced adsorption and separation of low concentration coalbed methane based on synergistic effect between FeTPPs and CuBTC[J]. CIESC Journal, 2022, 73(9): 3940-3949.
7	韩素英, 韩新华, 曹运祥, 等. 金属有机框架材料HKUST-1吸附分离CH₄/N₂性能研究[J]. 石油炼制与化工, 2018, 49(5): 43-48.
	HAN Suying, HAN Xinhua, CAO Yunxiang, et al. Adsorption separation of ch₄/n₂ over metal organic frame material hkust-1 [J]. Petroleum Processing and Petrochemicals, 2018, 49(5): 43-48.
8	李想, 张佳瑾, 李建伟. 含不饱和金属位点的金属有机骨架材料对¹⁴CH₄/N₂吸附分离行为的分子模拟研究[J]. 化工新型材料, 2021, 49(11): 192-197.
	LI Xiang, ZHANG Jiajin, LI Jianwei. Molecular simulation of adsorption and separation of ¹⁴CH₄/N₂ on MOFs containing open-metal sites[J]. New Chemical Materials, 2021, 49(11): 192-197.
9	李艳丽, 秦铭杉, 韦冬微, 等. UiO66的氨基化修饰及表征[J]. 天津农学院学报, 2023, 30(1): 59-63.
	LI Yanli, QIN Mingshan, WEI Dongwei, et al. Amination modification and characterization of UiO66[J]. Journal of Tianjin Agricultural University, 2023, 30(1): 59-63.
10	ZAHID Muhammad, ZHANG Dongxiang, XU Xiyan, et al. Barbituric and thiobarbituric acid-based UiO-66-NH₂ adsorbents for iodine gas capture: Characterization, efficiency and mechanisms[J]. Journal of Hazardous Materials, 2021, 416: 125835.
11	MOLAVI Hossein, ESKANDARI Alireza, SHOJAEI Akbar, et al. Enhancing CO₂/N₂ adsorption selectivity via post-synthetic modification of NH₂-UiO-66(Zr)[J]. Microporous and Mesoporous Materials, 2018, 257: 193-201.
12	余翔, 韩铭, 杨小震. 分子动力学模拟研究线型聚乙烯链在强电场中的取向行为[J]. 高等学校化学学报, 2011, 32(1): 180-184.
	YU Xiang, HAN Ming, YANG Xiaozhen. Molecular dynamics simulation study on the reorientation behavior of linear polyethylene under high electric field[J]. Chemical Journal of Chinese Universities, 2011, 32(1): 180-184.
13	卢天, 陈飞武. 原子电荷计算方法的对比[J]. 物理化学学报, 2012, 28(1): 1-18.
	LU Tian, CHEN Feiwu. Comparison of computational methods for atomic charges[J]. Acta Physico-Chimica Sinica, 2012, 28(1): 1-18.
14	HU Jianbo, LIU Yang, LIU Jing, et al. High CO₂ adsorption capacities in UiO type MOFs comprising heterocyclic ligand[J]. Microporous and Mesoporous Materials, 2018, 256: 25-31.
15	AZITA A K, SAEID Y. Computational study of the effect of functionalization on natural gas components separation and adsorption in NUM-3a MOF[J]. Journal of Molecular Graphics and Modelling, 2020, 101: 107731.
16	石勤, 席静, 张富民. MER型沸石吸附分离CO₂/CH₄的分子模拟[J]. 化工进展, 2020, 39(11): 4408-4417.
	SHI Qin, XI Jing, ZHANG Fumin. Molecular simulation of adsorption separation of CO₂/CH₄ by MER-type zeolites[J]. Chemical Industry and Engineering Progress, 2020, 39(11): 4408-4417.
17	邹龙辉. 氦基混合气体在活性炭中低温吸附特性研究[D]. 北京: 中国科学院理化技术研究所, 2018.
	ZOU Longhui. Research on cryogenic adsorption of helium-based gas mixture on activated carbon[D]. Beijing: Technical Institute of Physics and Chemistry CAS, 2018.
18	SIMON C M, SMIT B, HARANCZYK M. pyIAST: Ideal adsorbed solution theory (IAST) Python package[J]. Computer Physics Communications, 2016, 200: 364-380.
19	胡彪. 煤中多尺度孔隙结构的甲烷吸附行为特征及其微观影响机制[D]. 徐州: 中国矿业大学, 2022.
	HU Biao. Characteristics of methane adsorption behavior with multi-scale pore structure in coal and its micro-influence mechanism[D]. Xuzhou: China University of Mining and Technology, 2022.
20	杜晓明, 黄勇, 张倩, 等. NaX沸石吸附储氢的分子模拟[J]. 石油学报(石油加工), 2012, 28(S1): 137-140.
	DU Xiaoming, HUANG Yong, ZHANG Qian, et al. Molecular simulation of hydrogen adsorption on NaX zeolite[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2012, 28(S1): 137-140.
21	许嘉楠, 李强, 秦玉才, 等. TON分子筛上丁烷异构体吸附行为的分子模拟[J]. 石油炼制与化工, 2022, 53(11): 46-53.
	XU Jianan, LI Qiang, QIN Yucai, et al. Molecular simulation of adsorption behavior of butane isomers in ton zeolite[J]. Petroleum Processing and Petrochemicals, 2022, 53(11): 46-53.
22	赵静, 刘添翼, 李强, 等. NaX分子筛吸附分离CO₂/CH₄的巨正则蒙特卡洛模拟[J]. 辽宁石油化工大学学报, 2023, 43(2): 13-19.
	ZHAO Jing, LIU Tianyi, LI Qiang, et al. Grand canonical Monte Carlo simulation of adsorption and separation performances of CO₂/CH₄ by NaX zeolite[J]. Journal of Liaoning Petrochemical University, 2023, 43(2): 13-19.
23	高江涛, 冉小波, 霍宇航. 常压下CH₄/N₂/CO₂在阜生矿煤样表面吸附热力学研究[J]. 煤炭技术, 2022, 41(8): 136-139.
	GAO Jiangtao, RAN Xiaobo, HUO Yuhang. Thermodynamics study on adsorption of CH₄/N₂/CO₂ on surface of fusheng coal sample at normal pressure[J]. Coal Technology, 2022, 41(8): 136-139.

[1]	陈崇明, 陈秋, 宫云茜, 车凯, 郁金星, 孙楠楠. 分子筛基CO₂吸附剂研究进展[J]. 化工进展, 2023, 42(S1): 411-419.
[2]	李世霖, 胡景泽, 王毅霖, 王庆吉, 邵磊. 电渗析分离提取高值组分的研究进展[J]. 化工进展, 2023, 42(S1): 420-429.
[3]	许春树, 姚庆达, 梁永贤, 周华龙. 共价有机框架材料功能化策略及其对Hg(Ⅱ)和Cr(Ⅵ)的吸附性能研究进展[J]. 化工进展, 2023, 42(S1): 461-478.
[4]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[5]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[6]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[7]	贺美晋. 分子管理在炼油领域分离技术中的应用和发展趋势[J]. 化工进展, 2023, 42(S1): 260-266.
[8]	廖志新, 罗涛, 王红, 孔佳骏, 申海平, 管翠诗, 王翠红, 佘玉成. 溶剂脱沥青技术应用与进展[J]. 化工进展, 2023, 42(9): 4573-4586.
[9]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[10]	杨莹, 侯豪杰, 黄瑞, 崔煜, 王兵, 刘健, 鲍卫仁, 常丽萍, 王建成, 韩丽娜. 利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附[J]. 化工进展, 2023, 42(9): 5011-5018.
[11]	潘宜昌, 周荣飞, 邢卫红. 高效分离同碳数烃的先进微孔膜：现状与挑战[J]. 化工进展, 2023, 42(8): 3926-3942.
[12]	张振, 李丹, 陈辰, 吴菁岚, 应汉杰, 乔浩. 吸附树脂对唾液酸的分离纯化[J]. 化工进展, 2023, 42(8): 4153-4158.
[13]	姜晶, 陈霄宇, 张瑞妍, 盛光遥. 载锰生物炭制备及其在环境修复中应用研究进展[J]. 化工进展, 2023, 42(8): 4385-4397.
[14]	于静文, 宋璐娜, 刘砚超, 吕瑞东, 武蒙蒙, 冯宇, 李忠, 米杰. 一种吲哚基超交联聚合物In-HCP对水中碘的吸附作用[J]. 化工进展, 2023, 42(7): 3674-3683.
[15]	欧阳素芳, 周道伟, 黄伟, 贾凤. 新型耐迁移橡胶防老剂的研究进展[J]. 化工进展, 2023, 42(7): 3708-3719.

两种MOFs材料用于O₂/He吸附分离的模拟分析

Simulation analysis of two MOFs materials for O₂/He adsorption separation

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 23

相关文章 15

编辑推荐

Metrics

本文评价